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CN101878327A - Low-energy electrochemical hydroxide system and method - Google Patents

Low-energy electrochemical hydroxide system and method Download PDF

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Publication number
CN101878327A
CN101878327A CN200880118401XA CN200880118401A CN101878327A CN 101878327 A CN101878327 A CN 101878327A CN 200880118401X A CN200880118401X A CN 200880118401XA CN 200880118401 A CN200880118401 A CN 200880118401A CN 101878327 A CN101878327 A CN 101878327A
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ionogen
anode
negative electrode
exchange membrane
voltage
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D·W·柯克
J·D·维
A·J·巴德
R·J·吉利亚姆
K·法萨
V·德克
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Arelac Inc
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Calera Corp
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/24—Halogens or compounds thereof
    • C25B1/26—Chlorine; Compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/14—Alkali metal compounds
    • C25B1/16—Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/32—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00
    • B01D53/326—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by electrical effects other than those provided for in group B01D61/00 in electrochemical cells
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/402—Alkaline earth metal or magnesium compounds of magnesium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2251/00—Reactants
    • B01D2251/40—Alkaline earth metal or magnesium compounds
    • B01D2251/404—Alkaline earth metal or magnesium compounds of calcium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

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  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

In electrochemical cell, form the low energy method and system of hydroxide ion.When between anode and negative electrode, applying low voltage, in containing the ionogen of negative electrode, form hydroxide ion, on anode, form proton, but on anode, do not form gas for example chlorine or oxygen.

Description

Low-energy electrochemical hydroxide system and method
Background of invention
In many chemical technologies, need hydroxide ion (OH -) solution to realize or to regulate chemical reaction.In solution, obtain OH -A kind of mode be that alkali metal hydroxide such as sodium hydroxide or magnesium hydroxide are dissolved in the solution.But the traditional method of preparation oxyhydroxide is very highly energy-consuming, and the carbonic acid gas that for example chloralkali process, and their dischargings is a large amount of and other greenhouse gases are in environment.
Summary of the invention
In the various embodiments, the present invention relates in electrochemical cell, utilize ion-exchange membrane to produce OH -The low-energy electrochemical system and method.In a kind of embodiment, this system comprises negatively charged ion or the cationic exchange membrane between first ionogen and second ionogen, this first ionogen contact anode and second ionogen contact negative electrode.Suitable ionogen comprises salt solution (saltwater), and it comprises sodium-chlor, seawater, little Cheng Shui (brackish) or fresh water (fresh water).When between anode and negative electrode, applying low voltage, form OH at the negative electrode place -And form proton at the anode place, do not form gas for example chlorine or oxygen simultaneously at the anode place.Depend on used ionogen, in second ionogen that contacts with negative electrode, form for example sodium hydroxide of hydroxide solution, and in first ionogen that contacts with anode, form for example hydrochloric acid of acid.In the various embodiments, form OH when between electrode, applying the voltage less than 0.1V -
In another embodiment, this system comprises electrochemical cell, and wherein anion-exchange membrane is separated first ionogen and the 3rd ionogen; Cationic exchange membrane is separated the 3rd ionogen and first ionogen; Anode contacts with first ionogen; And negative electrode contacts with second ionogen.When between anode and negative electrode, applying low voltage, form OH at the negative electrode place -, do not form gas for example chlorine or oxygen simultaneously at the anode place.Depend on used ionogen, in second ionogen that contacts with negative electrode, form for example sodium hydroxide of hydroxide solution, and in first ionogen that contacts with anode, form for example hydrochloric acid of acid.In the various embodiments, form OH when between electrode, applying the voltage less than 0.1V -
In a kind of embodiment, this method comprises by applying voltage to form hydroxide ion at the negative electrode place between anode and negative electrode, simultaneously do not form gas for example chlorine or oxygen, pass the ion-exchange membrane migration ion between first ionogen and second ionogen at the anode place.Depend on used ionogen, in second ionogen that contacts with negative electrode, form for example sodium hydroxide of hydroxide solution, and in first ionogen that contacts with anode, form for example hydrochloric acid of acid.In the various embodiments, form OH when between electrode, applying the voltage less than 0.1V -
In another embodiment, this method is included between anode and the negative electrode and applies voltage, and wherein (i) this anode contacts with first ionogen, and this first ionogen contacts with anion-exchange membrane again; (ii) this negative electrode contacts with second ionogen, and this second ionogen contacts with cationic exchange membrane again; (iii) the 3rd ionogen forms hydroxide ion thus at the negative electrode place between anion-exchange membrane and cationic exchange membrane, does not form gas for example chlorine or oxygen simultaneously at the anode place.By this method, form OH at the negative electrode place that contacts with second ionogen -, do not form gas for example chlorine or oxygen simultaneously at the anode place.Depend on used ionogen, in second ionogen that contacts with negative electrode, form for example sodium hydroxide of hydroxide solution, and in first ionogen that contacts with anode, form for example hydrochloric acid of acid.In the various embodiments, form OH when between electrode, applying the voltage less than 0.1V -
Under the various configurations, this system and method is suitable for intermittence, semi-batch or continuous flow.Depend on used ionogen, this system can be suitable for forming OH in solution -The sodium hydroxide of negative electrode place (for example) or the acidic solution hydrochloric acid of anode place (for example) do not form gas for example chlorine or oxygen simultaneously at the anode place.In the various embodiments, can comprise OH by making -Solution and CO 2Contact and from the solution that comprises alkaline-earth metal ions for example carbonate and the supercarbonate of calcium and magnesium of precipitation alkaline earth metal carbonate, this solution is used for isolating CO 2As the U.S. Provisional Patent Application No.60/931 that submitted on May 24th, 2007,657, the U.S. Provisional Patent Application No.60/937 that submitted on June 28th, 2007,786, the U.S. Provisional Patent Application No.61/017 that submitted on December 28th, 2007,419, the U.S. Provisional Patent Application No.61/017 that submitted on December 28th, 786,2007,371, the U.S. Provisional Patent Application No.61/081 that submitted on July 16th, 2008 described in 299, is introduced into herein as a reference.In the various embodiments, sedimentary carbonate can be used as for example cement of building products, as described in as a reference the U.S. Patent application in being incorporated herein.Similarly, this system and method can be suitable for making water desalination, as described in as a reference the U.S. Patent application in being incorporated herein.
Description of drawings
The following accompanying drawing mode non-limiting by example set forth system and method for the present invention.By with reference to the one or more of these accompanying drawings and in conjunction with herein explanation, can understand this method and system better:
Fig. 1 is the synoptic diagram of system implementation mode of the present invention.
Fig. 2 is the synoptic diagram of system implementation mode of the present invention.
Fig. 3 is the synoptic diagram of system implementation mode of the present invention.
Fig. 4 is the synoptic diagram of system implementation mode of the present invention.
Fig. 5 is the synoptic diagram of system implementation mode of the present invention.
Fig. 6 is the synoptic diagram of system implementation mode of the present invention.
Fig. 7 is the schema of the inventive method embodiment.
Fig. 8 is the schema of the inventive method embodiment.
Describe in detail
Before describing the inventive method and system in detail, should be appreciated that the present invention is defined in to describe and illustrational specific implementations herein, and so can change.It is also understood that terminology used herein only is to be in the purpose of describing specific implementations, and be not to be to limit, because the scope of the invention is only defined by the appended claims.
When numerical range is provided, unless should be appreciated that on the contrary clear pointing out, otherwise any other the described value in this scope bound and this described scope or each intermediate value between the intermediate value (to lower limit unit 1/10th) be included within the present invention.Within these bounds more among a small circle can be included in more independently, and be also contained within the present invention, except within described scope, there being the concrete arbitrarily restriction of getting rid of.When described scope comprised limit one or both of, the scope of getting rid of these limits one or both of was also contained within the present invention.
Sometimes scope is expressed as numerical value titled with term " about " herein.Term " about " is used to provide its literal support of perfect number afterwards in this article, and the numerical value of counting after approaching or approximate this term.Determine numerical value whether near or during the approximate numerical value of specifically quoting, near and/or approximate unreferenced numerical value can be that the substantive numerical value of equal value of specifically quoting numerical value is provided in the context of its appearance.
Unless point out on the contrary, otherwise all technology used herein and scientific terminology all have the identical meanings that those of ordinary skill is understood in the affiliated field of the present invention.Also can be used for enforcement of the present invention or test though be similar to or be equivalent to described those any means, system and material herein, describe method, system and the material of exemplary illustration herein.
During all documents quoted in this specification sheets and patent are incorporated herein as a reference, be shown as particularly and individually as each independent document or patent and be incorporated herein by reference, and those come together disclosure and description method and/or materials to be quoted with the document as a reference in being incorporated herein.Quote with the disclosure before the applying date during reference citation arbitrarily, and do not think because invention the present invention formerly can not authorize with prior to the document.In addition, the date of the document that provides can be different from the actual date of publication, and can need independently to prove.
Herein with claims in, singulative " (a) ", " one (an) ", " this (the) " comprise plural form, unless context is clearly pointed out on the contrary.In addition, claim can be described as getting rid of any option unit.So, this explanation be intended to as use this removing property term as " individually ", " only " etc. and as described in the claim unit, the prerequisite basis of perhaps using " negating " qualification.In addition, surround such as container, jar, chamber or the bag that receiving fluids is used represented in term used herein " container ".
As those of ordinary skills are expressly understood, describe herein and illustrational every kind of embodiment comprise can with the feature of other various embodiments arbitrarily mutually independently or mutual completely different unit and the feature that makes up, do not deviate from scope of the present invention or spirit.Any described method can be carried out with the order of described incident or with any possible logical order.
During this paper describes, for easy, the present invention will be described aspect the generation hydroxide radical.To understand, can not produce hydroxide radical in some embodiments, for example the pH that makes the electrolyte solution that contacts with negative electrode (as described herein) keep constant or even when reducing, do not have clean production hydroxy, and can or even the hydroxide ion reduction of producing.This point can be for example with CO 2Introduce in the embodiment in second electrolyte solution and take place, as further describing herein.
In the various embodiments, the present invention relates to for example utilize ion-exchange membrane to form OH in the salt brine solution at solution -The low-energy electrochemical system and method.When between anode and negative electrode, applying voltage, with ionogen that negative electrode contacts in solution in form OH -, with solution that anode contacts in form proton, and do not form gas for example chlorine or oxygen at the anode place.The voltage that applies between anode and the negative electrode forms hydroxide ion less than 2.8,2.7,2.5,2.4,2.3,2.2,2.1,2.0,1.9,1.8,1.7,1.6,1.5,1.4,1.3,1.2,1.1,1.0,0.9,0.8,0.7,0.6,0.5,0.4,0.3,0.2 or during 0.1V.
In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 2.5V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 2.2V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 2.0V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 1.5V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 1.0V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.8V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.7V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.6V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.5V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.4V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.3V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.2V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.1V, does not form gas at the anode place simultaneously.In some embodiments, the voltage that applies between anode and the negative electrode forms hydroxide ion during less than 0.05V.In the various embodiments, with ionogen that anode contacts in form for example hydrochloric acid of acidic solution.
With reference to Fig. 1-6, in the various embodiments, the present invention is suitable for intermittence and continuous processing as described herein.With reference to Fig. 1 and 2, this system comprises electro-chemical systems in a kind of embodiment, it comprises first ionogen (104) and the separated ion-exchange membrane of second ionogen (106) (102,124), this first ionogen contact anode (108) and second ionogen contact negative electrode (110)." ion-exchange membrane " used herein comprises the film of an ion of alternative infiltration or a class ion (for example negatively charged ion or monovalent anion, perhaps positively charged ion or univalent cation).In the system shown in Figure 1, when between anode and negative electrode, applying voltage, with ionogen that negative electrode contacts in form hydroxide ion, with ionogen that anode contacts in form proton, do not form gas for example chlorine or oxygen simultaneously at the anode place.In Fig. 1 example, adopted anion-exchange membrane (102); Among Fig. 2, adopted cationic exchange membrane (124).
In the system shown in Figure 1, first ionogen (104) comprises aqueous salt solution such as salt solution (saltwater), for example seawater, fresh water (fresh water), brackish water (brine), slightly salty (brackish) etc.In the various embodiments, second ionogen (106) comprises the concentrated solution of sodium-chlor, and in other embodiment, second ionogen can Bao Weicheng water.In Fig. 2 embodiment, first ionogen (104) comprises the concentrated solution of sodium-chlor, and second ionogen (106) comprises aqueous solution such as salt solution, for example seawater, fresh water, brackish water, slightly salty etc.In the embodiment of replacing, first ionogen can comprise salt solution.
In the various embodiments, anion-exchange membrane (102) and/or cationic exchange membrane (124) can be that to be suitable for temperature range be about 0～about 100 ℃ acidity and/or any ion-exchange membrane of alkaline electrolyte solution, conventional ion exchange membrane, the perhaps ion-exchange membrane of any suitable as known in the art.Suitable ion-exchange membrane can obtain from the PCA GmbH of Germany, for example can use the anion-exchange membrane of the trade mark as PCSA-250-250; Similarly, can use the trade mark that can obtain from PCAGmbH cationic exchange membrane as PCSK-250-250.To understand, ion-exchange membrane will be located in this system to prevent the first and second electrolytical mixing.
With reference to Fig. 1 and 2, in the various embodiments, electro-chemical systems (100,200) comprises the second ionogen inlet end (116) that is used for that first ionogen (104) injected the first ionogen inlet end (114) of this system and is used for second ionogen (106) is injected this system.This pond comprises and is used for discharging the first electrolytical exit end (118) and being used for discharging the second electrolytical exit end (120) from this system from this system.As those of ordinary skill was understood, this entrance and exit end can be suitable for various flow pattern, comprised intermittent flow, semi-batch stream or Continuous Flow.In the embodiment of replacing, this system comprises and being used for the hydrogen for example transfer lime (122) of anodic conduit that leads; In the various embodiments, this gas is included in the hydrogen that negative electrode (110) is located to form; Can use other sources of hydrogen.
As shown in figs. 1 and 2, first ionogen (104) contacts anode (108) and contact ions exchange membrane (102,124) on first side; And second ionogen contact negative electrode (106) and on opposite side the contact ions exchange membrane, finish the circuit that comprises conventional voltage/current regulator (112) thus.This voltage/current regulator can be suitable for increasing or reduce the curtage between negative electrode and the anode, and is as desired.
With reference to Fig. 1, in using anion-exchange membrane (102) and the exemplary and non-limiting example of sodium-chlor concentrated solution as second ionogen (116), when between negative electrode (110) and anode (108), applying low voltage, in second ionogen, form hydroxide ion and locate to form hydrogen at negative electrode (110), simultaneously with first electrolyte solution that anode (108) contact in form proton, still locate not form gas for example chlorine or oxygen at anode (108).Second ionogen (106) is when comprising sodium-chlor, and chlorion is moved to first ionogen (104) through anion-exchange membrane (102) from second ionogen (106), and with ionogen that anode (108) contacts in form proton.
As one of ordinary skill will be appreciated, and with reference to Fig. 1, in second ionogen (106) since hydroxide ion with ionogen that negative electrode (110) contact in formation and enter second ionogen (106), and since chlorion from second electrolyte to first ionogen (104), in second ionogen (106) formation sodium hydroxide aqueous solution.Depend on the speed that second ionogen (106) is introduced this system and/or therefrom discharged, the second electrolytical pH is adjusted, and for example increases, reduction or constant.Similarly, with reference to Fig. 1 since proton with solution that anode contact in form and enter first ionogen (104), the first electrolytical pH will adjust, and depend on first ionogen is introduced this system and/or the speed of discharge therefrom.In addition and since chlorion pass anion-exchange membrane from second electrolyte to first ionogen, in first ionogen, form hydrochloric acid.
With reference to Fig. 2, in another exemplary and indefiniteness embodiment, when using cationic exchange membrane (124) and using the sodium-chlor concentrated solution as first ionogen, when between negative electrode (110) and anode (108), applying voltage, in second ionogen, form hydroxide ion and locate to form hydrogen at negative electrode (110), in first ionogen that contacts with anode, form proton, but locate not form gas such as chlorine or oxygen at anode (108).First ionogen (104) is when comprising sodium-chlor, and sodium ion is moved to second ionogen (106) through cationic exchange membrane (124) from first ionogen (104).
As one of ordinary skill will be appreciated, and with reference to Fig. 2, in second ionogen (106) since hydroxide ion with ionogen that negative electrode (110) contact in formation and enter solution, and, in second ionogen (106), form the aqueous solution of sodium hydroxide because sodium ion is moved to second ionogen.Depend on the speed that second ionogen is introduced this system and/or therefrom discharged, the second electrolytical pH is adjusted, and for example increases, reduction or constant.Similarly, with reference to Fig. 1 and since proton with solution that anode contact in formation and enter solution, the first electrolytical pH will adjust, depend on the speed that first ionogen is introduced this system and/or therefrom discharged, promptly the first electrolytical pH can increase, reduction or constant.In addition, since sodium ion pass cationic exchange membrane from first electrolyte to second ionogen, because the existence of proton and chlorion in first ionogen will form hydrochloric acid in first ionogen.
With reference to Fig. 1 and 2, depend on electrolytical flowing and used ionogen salt solution for example in the system, when between anode (108) and negative electrode (110), applying voltage, will in second ionogen (106), form OH -, and cause the second electrolytical pH to be adjusted thus.In a kind of embodiment, between anode and negative electrode, apply about 0.1V or lower, 0.2V or lower, 0.4V or lower, 0.6V or lower, 0.8V or lower, 1.0V or lower, 1.5V or lower or 2.0V or lower voltage, for example when 0.8V or lower voltage, the pH of second electrolyte solution increases; In another embodiment, between anode and negative electrode, apply the voltage of 0.01～2.5V or 0.01V～2.0V or 0.1V～2.0V or 0.1V～1.5V or 0.1V～1.0V or 0.1V～0.8V or 0.1V～0.6V or 0.1V～0.4V or 0.1V～0.2V or 0.01V～1.5V or 0.01V～1.0V or 0.01V～0.8V or 0.01V～0.6V or 0.01V～0.4V or 0.01V～0.2V or 0.01V～0.1V, for example during the voltage of 0.1～2.0V, the second electrolytical pH increases; Still in another embodiment, when applying the voltage of about 0.1～1V between anode and negative electrode, the pH of second electrolyte solution increases.Between electrode, adopt the voltage of 0.1～0.8V, 0.1～0.7V, 0.1～0.6V, 0.1～0.5V, 0.1～0.4V and 0.1～0.3V can obtain similar results.Summarized the example results that adopts system of the present invention to realize in the table 1.
Table 1 low-energy electrochemical method and system
Voltage between the electrode Film type Mean current Initial pH anode and negative electrode The final pH anode The final pH negative electrode
??0.4 Negatively charged ion ??1.45 ??6.624 ??4.790 ??9.609
??0.6 Negatively charged ion ??1.27 ??6.624 ??4.643 ??9.779
Voltage between the electrode Film type Mean current Initial pH anode and negative electrode The final pH anode The final pH negative electrode
??0.4 Negatively charged ion ??0.81 ??6.624 ??4.896 ??9.458
??0.6 Negatively charged ion ??0.90 ??6.624 ??4.596 ??9.393
??1.0 Negatively charged ion ??1.49 ??6.624 ??4.677 ??9.974
??0.6 Positively charged ion ??2.07 ??6.624 ??4.444 ??10.140
??0.6 Positively charged ion ??16.0 ??6.624 ??3.381 ??11.171
??1.0 Positively charged ion ??24.7 ??6.624 ??3.245 ??11.328
??1.0 Positively charged ion ??14.0 ??6.624 ??3.237 ??10.901
??0.6 Positively charged ion and negatively charged ion ??6.22 ??6.624 ??3.888 ??10.717
??1.0 Positively charged ion and negatively charged ion ??17.6 ??6.624 ??3.115 ??11.066
With reference to table 1, use salt solution as first ionogen and sodium-chlor as second ionogen, shown in Fig. 1,2 or 3, be used for regulating pH in first and second ionogen according to technology of the present invention and method.By this method and system, with operating voltage low between the electrode, in second ionogen (106), produce NaOH, and in first ionogen (104), produce hydrochloric acid; Such as one of ordinary skill understood, voltage can be heightened or turn down from these exemplary voltage; Minimum theoretical voltage is 0 or is in close proximity to 0, but in order to realize useful hydroxide radical throughput rate, actual lower limit can be 0.001V or 0.01V or 0.1V in some embodiments, depends on clearly other factors of the volume of the hydroxide radical production of expectation and/or pH condition time, second electrolyte solution and those of ordinary skill; That is, in some embodiments, this system and method can produce hydroxide radical under the voltage that is low to moderate 0.001V or 0.01V or 0.1V, and if also can for example under 0.2～2.0V, produce hydroxide radical at high-voltage more during the quicker production of expectation; Produce hydroxide radical in some embodiments, do not form gas at the anode place simultaneously, for example do not form oxygen or chlorine.
System for use in carrying comprises two 250mL compartments, and it is separated by anion-exchange membrane in one embodiment, and is separated by cationic exchange membrane in another embodiment.Use 0.5M NaCl 18M Ω aqueous solution (with the NaCl deionized water solvation of 28g/L) in two compartments.The two comprises 10cm * 5cm 45 order Pt nets anode and negative electrode.In the anode compartment, below the Pt electrode, spray H 2Gas, and make two electrodes remain on bias voltage as shown in table 1 (for example 0.4,0.6V and 1.0V) following 30 minutes.Applying the electrolytical pH that contacts with anode before the voltage is 6.624.The negative electrode compartment that hydroxide radical formation wherein takes place stirs with 600rpm.As shown in table 1, in negative electrode and anode compartment, realize the noticeable change of pH.
In these examples, and in the various embodiment of the present invention, between anode and negative electrode, apply 1.0V or lower, 0.9V it is or lower, 0.8V it is or lower, 0.7V it is or lower, 0.6V it is or lower, 0.5V it is or lower, 0.4V it is or lower, 0.3V it is or lower, 0.2V it is or lower, 0.1V it is or lower, perhaps when 0.05V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce greater than 0.5,1.0,1.5,2.0,2.5,3.0,3.5,4.0,4.5,5.0,5.5,6,6.5,7.0,7.5,8.0,8.5,9.0,9.5,10.0,10.5,11.0,11.5, or the pH difference of 12.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.
For example, in the specific implementations, the invention provides when between anode and negative electrode, applying 0.05V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 0.5pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.In some embodiments, the invention provides when between anode and negative electrode, applying 0.1V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 1.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.In some embodiments, the invention provides when between anode and negative electrode, applying 0.2V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 2.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.
In some embodiments, the invention provides when between anode and negative electrode, applying 0.4V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 4.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.In some embodiments, the invention provides when between anode and negative electrode, applying 0.6V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 6.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.In some embodiments, the invention provides when between anode and negative electrode, applying 0.8V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 8.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.In some embodiments, the invention provides when between anode and negative electrode, applying 1.0V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 8.0pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.In some embodiments, the invention provides when between anode and negative electrode, applying 1.2V or lower voltage, can in first electrolyte solution and second electrolyte solution, produce system greater than the pH difference of 10pH unit, wherein first electrolyte solution contact anode and second electrolyte solution contact negative electrode, and two electrolyte solutions are for example separated by one or more ion-exchange membranees.
To understand, it is constant that voltage needn't keep, and at two electrolytical pH identical or pH near the time, the voltage that applies between anode and the negative electrode can be extremely low, 0.05V or lower for example, and voltage can increase when needs pH difference increases.Like this, can realize the pH difference or the hydroxide ion production of expectation with minimum average B configuration voltage.Thus, in some embodiments, as described in the previous paragraph, average voltage can than little by 80% in the first previous paragraphs about the described voltage of specific implementations, 70%, 60% or little by 50%.
In the various embodiments and with reference to Fig. 1-2, the hydrogen guiding anode (108) that will locate to form in negative electrode (110).Be not bound by any theory, think that this gas is absorbed and/or absorbs anode and forms proton subsequently at the anode place.
In some embodiments, in the part process when ionogen and ion-exchange membrane (a plurality of films, the described embodiment that wherein uses an above film vide infra) contact, the divalent cation of one or more electrolyte solutions is consumed, for example magnesium or calcium.Do like this is in order to prevent the fouling of film, if necessary for those specific films.Thus, in some embodiments, wherein the total concn of divalent cation is less than 0.06mol/kg solution or less than 0.06mol/kg solution or less than 0.04mol/kg solution or less than 0.02mol/kg solution or less than 0.01mol/kg solution or less than 0.005mol/kg solution or less than 0.001mol/kg solution or less than 0.0005mol/kg solution or less than 0.0001mol/kg solution or less than 0.00005mol/kg solution when electrolyte solution contacts the time that perceives arbitrarily with ion-exchange membrane or a plurality of film.
In another embodiment as shown in Figure 3, system of the present invention (300) comprises the ionogen pond of containing the anode (108) that contacts with first ionogen (104); With first ionogen and the separated anion-exchange membrane of the 3rd ionogen (130) (102); Second ionogen of contact negative electrode (110); With with second ionogen and the separated cationic exchange membrane of the 3rd ionogen (124).Be appreciated that this ion-exchange membrane is located in this system to prevent the first and second electrolytical mixing.Current/voltage setter (112) can be suitable for increasing or the reduction system in curtage between negative electrode and the anode, as desired.When between anode and negative electrode, applying voltage, with ionogen that negative electrode contacts in form hydroxide ion, do not form gas for example chlorine or oxygen simultaneously at the anode place.As the system of Fig. 1 and 2, the system of Fig. 3 can be suitable for intermittence, semi-batch and operate continuously.
In the system shown in Figure 3, as the system of Fig. 1-2, first ionogen (104), second ionogen (106) and the 3rd ionogen (130) comprise for example salt solution in the various embodiments, comprise seawater, fresh water, brackish water or slightly salty etc.In a kind of embodiment, the 3rd ionogen (130) comprises sodium chloride solution in fact.
In the various embodiments, the anion-exchange membrane of Fig. 3 (102) and/or cationic exchange membrane (124) can be that to be suitable for operating temperature range in the aqueous solution be about 0～about 100 ℃ or higher acidity and/or any ion-exchange membrane of basic solution, depend on the pressure in the system, conventional ion exchange membrane, the perhaps ion-exchange membrane of any suitable as known in the art.Suitable ion-exchange membrane can obtain from the PCA GmbH of Germany, for example can use the anion-exchange membrane of the trade mark as PCSA-250-250; Similarly, can use the trade mark that can obtain from PCA GmbH cationic exchange membrane as PCSK-250-250.
With reference to Fig. 3, in the various embodiments, electrochemical cell comprises the first ionogen inlet end (114) that is used for first ionogen (104) is injected this system; Be used for second ionogen (106) is injected the second ionogen inlet end (116) of this system; With the 3rd inlet end (126) that is used for the 3rd ionogen is injected this system.In addition, this pond comprises and is used for discharging first electrolytical first exit end (118) from this system; Be used for discharging second electrolytical second exit end (120) from this system; Get rid of the 3rd electrolytical the 3rd exit end (128) with being used for from this system.As those of ordinary skill was understood, this entrance and exit end can be suitable for various flow pattern, comprised intermittent flow, semi-batch stream or Continuous Flow.In the embodiment of replacing, this system comprises and being used for the hydrogen for example transfer lime (122) of anodic conduit that leads; In the various embodiments, this gas is included in the hydrogen that negative electrode (110) is located to form.
With reference to Fig. 3, when between negative electrode (110) and anode (108), applying voltage, with ionogen that negative electrode (110) contacts in form hydroxide ion, with ionogen that anode contacts in form hydroxide ion, and do not form gas for example chlorine or oxygen in anode place (108).The 3rd ionogen (130) is when comprising sodium-chlor, and chlorion is moved to first ionogen (104) through anion-exchange membrane (102) from the 3rd ionogen (130); Sodium ion is moved to second ionogen (106) from the 3rd ionogen (130); Form proton in anode place (108); And form hydrogen in negative electrode place (110).
What one of ordinary skill in the art will appreciate that is such, and with reference to Fig. 3, since hydroxide ion with ionogen that negative electrode (110) contact in formation and enter the 3rd ionogen, chlorion is moved to second ionogen (106) from the 3rd ionogen (130) simultaneously, forms the aqueous solution of sodium hydroxide in second ionogen (106).Depend on the voltage that applies between the system and with the flow velocity of second ionogen through this system, the pH of this solution will adjust.In a kind of embodiment, when applying about 0.1V or lower, 0.2V or lower, 0.3V or lower, 0.4V or lower, 0.5V or lower, 0.6V or lower, 0.7V or lower, 0.8V or lower, 0.9V or lower, 1.0V or lower, 1.2V or lower, 1.4V or lower, 1.6V or lower, 1.8V or lower, 2.0V or lower or 2.2V or lower voltage between anode and negative electrode, the pH of second electrolyte solution increases; In another embodiment, between anode and negative electrode, apply the voltage of 0.01～2.5V or 0.01V～2.0V or 0.1V～2.0V or 0.1V～1.5V or 0.1V～1.0V or 0.1V～0.8V or 0.1V～0.6V or 0.1V～0.4V or 0.1V～0.2V or 0.01V～1.5V or 0.01V～1.0V or 0.01V～0.8V or 0.01V～0.6V or 0.01V～0.4V or 0.01V～0.2V or 0.01V～0.1V, for example during the voltage of 0.1～2.0V, the second electrolytical pH increases; Still in another embodiment, when applying the voltage of about 0.1～1V between anode and negative electrode, the pH of second electrolyte solution increases.Between electrode, adopt the voltage of 0.1～0.8V, 0.1～0.7V, 0.1～0.6V, 0.1～0.5V, 0.1～0.4V and 0.1～0.3V can obtain similar results.In a kind of embodiment, between anode and negative electrode, apply about 0.6V or lower voltage; In another embodiment, between anode and negative electrode, apply the voltage of about 0.1～0.6V; Still in another embodiment, between anode and negative electrode, apply the voltage of about 0.1～1V.
With the such of understanding and with reference to Fig. 3, in first ionogen (104), since proton with ionogen that anode (108) contact in formation and enter solution, chlorion is moved to first ionogen (104) from the 3rd ionogen (130) simultaneously, little by little forms acidic solution in first ionogen (104).Depend on the voltage that applies between the system and second ionogen flow velocity through this system, the pH of this solution will adjust as described above.
As the embodiment of Fig. 1 and 2 and as shown in Figure 3, the hydrogen guiding anode (108) that randomly will locate to form in negative electrode (110).Be not bound by any theory, think that hydrogen is absorbed and/or absorbs anode and forms proton at the anode place that contacts with first ionogen (104) subsequently.In addition, in the various embodiments as Figure 1-3, do not form gas such as oxygen or chlorine in anode place (108).Thus, be appreciated that, in first ionogen (104), obtain hydrochloric acid owing to move to first ionogen at the formation and the chlorion of anode place proton.
With reference to Fig. 4, it has set forth the version of Fig. 3 embodiment, and cationic exchange membrane contacts with anode (108) on a surface, and contacts with first ionogen (104) on the apparent surface.Under this configuration, such as one of ordinary skill understood, the anode place or near the H+ of formation move to first ionogen through cationic exchange membrane, cause the first electrolytical pH to adjust thus, as reference Fig. 3 system is discussed.Similarly, locate at negative electrode (110), anion-exchange membrane contacts with anode (110) on a surface, and contacts with second ionogen (106) on the apparent surface.Under this configuration, such as one of ordinary skill understood, the anode place or near the OH of formation -To move to first ionogen, and cause the second electrolytical pH to adjust thus, as reference Fig. 3 system is discussed.Randomly, as shown in Figure 4, the hydrogen that negative electrode (110) can be located to form leads once more and does not contact second (106) or first (104) the electrolytical anode (108).
Fig. 5 has set forth version of the present invention, and wherein the system of at least two Fig. 4 of configuration is with operation together.As will be appreciated like that and with reference to Fig. 5, because hydroxide ion locates to form and enter second ionogen (106) at negative electrode (110), and sodium ion is moved to second ionogen from the 3rd ionogen (130), forms the aqueous solution of sodium hydroxide in second ionogen (106).Depend on electrolytical interpolation and/or rate of discharge in this system, the second electrolytical pH is adjusted, and for example increases, reduction or constant.In addition with reference to Fig. 5, in first ionogen (104), because proton locates to form and enter solution at anode (108), chlorion is moved to first ionogen (104) from the 3rd ionogen (130) simultaneously, little by little forms acidic solution in first ionogen (104).
Fig. 6 has set forth the version of Fig. 3 system, is arranged to continuous or semicontinuous flow pattern.With reference to Fig. 6, when between negative electrode (110) and anode (108), applying low voltage, locate to form hydroxide ion at negative electrode (110), form proton at the anode place, and locate not form gas such as chlorine or oxygen at anode (108).The 3rd ionogen (130) is when comprising sodium-chlor, chlorion is moved to first ionogen (104) through anion-exchange membrane (102) from the 3rd ionogen (130), sodium ion is moved to second ionogen (106) through cationic exchange membrane (124) from the 3rd ionogen (130), locate to form proton at anode (104), and locate to form hydrogen at negative electrode (110).In first ionogen (104), because proton locates to form and enter solution at anode (108), chlorion is moved to first ionogen (104) from the 3rd ionogen (130) simultaneously, little by little forms acidic solution in first ionogen (104).Depend on the voltage that applies between the system and second ionogen flow velocity through this system, the pH of this solution will adjust.
With reference to Fig. 1,2 and 7, in a kind of embodiment, the inventive method (700) comprises the steps (702): by applying voltage to form hydroxide ion at the negative electrode place between anode and negative electrode, simultaneously do not form gas at the anode place, through being positioned at ion-exchange membrane (102) the migration ion between first ionogen (104) and second ionogen (106), this first ionogen contacts with anode (108) and second ionogen contacts with negative electrode (110).As described in reference Fig. 1-2, because hydroxide ion locates to form and enter second ionogen (106) at anode (108), chlorion moves among second ionogen simultaneously, forms the aqueous solution of sodium hydroxide in second ionogen (106).Thus, depend on the voltage that applies between the system and second ionogen (106) flow velocity through this system, the second electrolytical pH will adjust.In addition, because proton forms in first ionogen, because chlorion moves to first ionogen and form acid solution in first ionogen, as the system of reference Fig. 1 and 2 is discussed.
In a kind of embodiment, when applying about 0.6V or lower voltage between anode and negative electrode, the second electrolytical pH increases; In another embodiment, when applying about 0.1～0.6V or lower voltage between anode and negative electrode, the second electrolytical pH increases.In another embodiment, when applying about 0.1～1V or lower voltage between anode and negative electrode, the second electrolytical pH increases.Summarized other example results that realizes according to system of the present invention in the table 1.
With reference to Fig. 3-6 and 8, in a kind of embodiment, the inventive method (800) comprises the steps (802): apply voltage between anode (108) and negative electrode (110), wherein (i) this anode contacts with first ionogen (104), and this first ionogen contacts with anion-exchange membrane (102) again; (ii) this negative electrode contacts with second ionogen (106), and this second ionogen contacts with cationic exchange membrane again; (iii) the 3rd ionogen (130) forms hydroxide ion thus at the negative electrode place between anion-exchange membrane and cationic exchange membrane, does not form gas at the anode place simultaneously.As above described with reference to Fig. 3-6 system, because hydroxide ion locates to form and enter second ionogen (106) at negative electrode (110), and sodium ion is moved to second ionogen from the 3rd ionogen (130), forms the aqueous solution of sodium hydroxide in second ionogen (106).Thus, depend on the voltage that applies between the system and second ionogen (106) flow velocity through this system, the second electrolytical pH will adjust.In addition since proton in first ionogen, form and chlorion from the 3rd electrolyte to first ionogen, in first ionogen, form acid solution.
In described in this article all embodiments, randomly, with CO 2Be dissolved in second electrolyte solution, owing to proton is discharged from second ionogen, can be with more CO 2With supercarbonate (root) and/or the dissolving of carbonate (root) ionic species, depend on the second electrolytical pH, be equilibrated at towards supercarbonate or towards the carbonate variation, as known in the art.In these embodiments, the second electrolytical pH can reduce, and remains unchanged, and perhaps increases, and depends on respect to CO 2Introduce the proton rate of discharge of speed.To understand, and need not to form hydroxide radical in these embodiments, perhaps hydroxide radical can not form in a stage but forms in another stage.Randomly, described herein another electro-chemical systems can be used to produce spissated oxyhydroxide, and it contains dissolved CO being added to 2Second ionogen in the time, cause carbonate and/or bicarbonate compound such as lime carbonate or magnesiumcarbonate and/or the sedimentary formation of their supercarbonate.In some embodiments, divalent cation such as magnesium and/or calcium are present in some used in this method solution, and/or with its adding.Sedimentary carbonate cpds can be used as cement and material of construction, as described in as a reference the U.S. Patent application in being incorporated herein.
In the optional step, acidifying first electrolyte solution 104 is used for solubilize calcium and/or magnesium rich ore, as comprises the femic minerals of serpentinite or peridotites, to precipitate aforesaid carbonate and supercarbonate.For example, the acidifying logistics can be used for solubilize calcium and/or magnesium rich ore such as serpentinite and peridotites, form thus can inject bicarbonate ion and subsequently fully alkalization with the electrolyte solution of precipitation carbonate cpds.As a reference U.S. Patent application during this precipitin reaction and the throw out purposes in cement is described in and is incorporated herein.
In the embodiment of replacing, be not precipitation carbonate, carbonate and bicarbonate solution are handled in its long-time stable place.For example, the carbonate electrolyte solution can be pumped into temperature and pressure and be enough to keep this solution stable deep-sea in the above-mentioned at least time period.
Though illustrate by way of example that for the clear purpose of understanding the mode with embodiment has described aforementioned invention in detail, but for considering instruction of the present invention, those of ordinary skills are understood that easily, can carry out some changes and improvements to it, not deviate from the spirit or scope of claims.
Thus, aforementionedly only set forth principle of the present invention.To understand, those of ordinary skills can design various arrangements, though its clearly description or demonstration in this article, but still embodied principle of the present invention, and comprise within its spirit and scope.In addition, the statement of the embodiment that quotes herein and situation is intended to help reader understanding's principle of the present invention and inventor's contribution to be used for promoting the idea of this area in principle, and does not constitute and be limited to specifically described like this embodiment and situation.In addition, describe herein the principle of the invention, aspect and embodiment with and all descriptions of specific embodiment, be intended to comprise its 26S Proteasome Structure and Function Equivalent the two.In addition, these Equivalents be intended to comprise present known Equivalent and exploitation in the future Equivalent the two, promptly develop any unit of carrying out identical function, do not consider structure.Thus, the scope of the invention is not to be defined in the illustrative embodiments that shows and describe herein.On the contrary, scope and spirit of the present invention are embodied by claims.

Claims (80)

1. electro-chemical systems, it comprises:
First ionogen, itself and second ionogen are separated, this first ionogen contact anode and second ionogen contact negative electrode, wherein,
When applying voltage between anode and negative electrode, this system can form hydroxide ion in second ionogen, does not form gas simultaneously on anode.
2. the system of claim 1, wherein this first ionogen and second ionogen are separated by ion-exchange membrane at least in part.
3. the system of claim 1, wherein, this system causes hydrogen to form at the negative electrode place in the time of can applying voltage between anode and negative electrode.
4. the system of claim 3, wherein this system further comprises and being used for the hydrogen anodic conduit that leads.
5. the system of claim 2, wherein this ion-exchange membrane comprises anion-exchange membrane.
6. the system of claim 2, wherein this second ionogen comprises salts solution, it comprises seawater, fresh water, brackish water or slightly salty.
7. the system of claim 2, wherein this first and second ionogen comprises seawater, fresh water, brackish water or slightly salty.
8. claim 6 or 7 method, wherein this second ionogen comprises sodium-chlor.
9. the system of claim 8, cause when wherein this system can apply voltage between anode and negative electrode chlorion through anion-exchange membrane from second electrolyte to first ionogen; Cause proton to form at the anode place; And cause hydrogen to form at the negative electrode place.
10. the system of claim 9 does not wherein form oxygen at the anode place.
11. the system of claim 9 does not wherein form chlorine at the anode place.
12. the system of claim 1, wherein this ion-exchange membrane comprises cationic exchange membrane.
13. the system of claim 1, wherein this second ionogen comprises salts solution, and it comprises seawater, fresh water, brackish water or slightly salty.
14. the system of claim 1, wherein this first and second ionogen comprises seawater, fresh water, brackish water or slightly salty.
15. the system of claim 13 or 14, wherein this seawater, fresh water, brackish water or slightly salty lack divalent cation.
16. the system of claim 13 or 14, wherein this first ionogen comprises sodium-chlor.
17. the system of claim 16, cause when wherein this system can apply voltage between anode and negative electrode sodium ion through cationic exchange membrane from first electrolyte to second ionogen; Cause proton to form at the anode place; And cause hydrogen to form at the negative electrode place.
18. the system of claim 17 does not wherein form oxygen at the anode place.
19. the system of claim 17 does not wherein form chlorine at the anode place.
20. the system of claim 9, wherein, when applying voltage between anode and negative electrode, this system can cause forming sodium hydroxide and cause forming hydrochloric acid in first ionogen in second ionogen.
21. the system of claim 17 wherein forms sodium hydroxide in second ionogen, and forms hydrochloric acid in first ionogen.
22. the system of claim 1 forms hydroxide radical when it can apply 0.6V or lower voltage between anode and negative electrode.
23. the system of claim 1 forms hydroxide radical when it can apply the voltage of 0.1～0.6V between anode and negative electrode.
24. the system of claim 1 forms hydroxide radical when it can apply the voltage of 0.1～1V between anode and negative electrode.
25. an electro-chemical systems, it comprises:
The first ionogen pond, it comprises the anode that contacts with first ionogen, and separates with the 3rd ionogen; With
The second ionogen pond, it comprises second ionogen that contacts with negative electrode, and separates with the 3rd ionogen;
Wherein, this system forms hydroxide ion in the time of can applying voltage between anode and negative electrode in second ionogen, does not form gas simultaneously on anode.
26. the electro-chemical systems of claim 25, wherein, this first ionogen and the 3rd ionogen are separated by anion-exchange membrane, and second ionogen and the 3rd ionogen are separated by cationic exchange membrane.
27. the electro-chemical systems of claim 25 causes hydrogen to form at the negative electrode place when wherein this system can apply voltage between anode and negative electrode.
28. the system of claim 25, it further comprises and being used for the hydrogen anodic conduit that leads.
29. the system of claim 26, wherein this anion-exchange membrane can permeate chlorion, and this cationic exchange membrane can permeate sodium ion.
30. the system of claim 29, wherein the 3rd ionogen comprises sodium-chlor.
31. the system of claim 30, wherein this first ionogen comprises salt solution, and it comprises seawater, fresh water, brackish water or slightly salty.
32. the system of claim 30, wherein this second ionogen comprises salt solution, and it comprises seawater, fresh water, brackish water or slightly salty.
33. the system of claim 32 or 33, wherein this salt olighydria divalent cation.
34. the system of claim 32 or 33, cause when wherein this system can apply voltage between anode and negative electrode chlorion through anion-exchange membrane from the 3rd electrolyte to first ionogen; Cause proton to form at the anode place; Cause sodium ion through cationic exchange membrane from the 3rd electrolyte to second ionogen; And cause hydrogen to form at the negative electrode place.
35. the system of claim 34 wherein forms hydrochloric acid in first ionogen.
36. the system of claim 34 causes forming sodium hydroxide in second ionogen when wherein this system can apply voltage between anode and negative electrode.
37. the system of claim 34 when wherein applying voltage between anode and negative electrode, does not form oxygen or chlorine at the anode place.
38. the system of claim 25 forms hydroxide radical when it can apply 0.1V or lower voltage between anode and negative electrode.
39. the system of claim 25 forms hydroxide radical when it can apply 0.1～about 0.4V or lower voltage between anode and negative electrode.
40. the system of claim 25 forms hydroxide radical when it can apply 0.1～about 0.6V or lower voltage between anode and negative electrode.
41. electrochemical method, it comprises by applying voltage to form hydroxide ion at the negative electrode place between anode and negative electrode, simultaneously do not form gas at the anode place, pass the ion-exchange membrane between first ionogen and second ionogen and move ion, this first ionogen contact anode and second ionogen contact negative electrode.
42. the method for claim 41, wherein this ion-exchange membrane comprises anion-exchange membrane.
43. the method for claim 42, wherein this second ionogen comprises sodium-chlor, and first ionogen comprises salt solution, and it comprises seawater, fresh water, brackish water or slightly salty.
44. the method for claim 43, wherein this salt olighydria divalent cation.
45. the method for claim 43, wherein chlorion through anion-exchange membrane from second electrolyte to first ionogen; Form hydrogen at the negative electrode place; And form proton at the anode place.
46. the method for claim 45, anode wherein leads hydrogen.
47. the method for claim 45 wherein forms sodium hydroxide in second ionogen, and forms hydrochloric acid in first ionogen.
48. the method for claim 41, wherein this ion-exchange membrane comprises cationic exchange membrane.
49. the method for claim 48, wherein this second ionogen comprises sodium-chlor.
50. the method for claim 49, wherein this first ionogen comprises salt solution, and it comprises seawater, fresh water, brackish water or slightly salty.
51. the method for claim 49, wherein sodium ion through cationic exchange membrane from first electrolyte to second ionogen; Form hydrogen at the negative electrode place; Form proton at the anode place.
52. the method for claim 51, anode wherein leads hydrogen.
53. the method for claim 51 wherein forms sodium hydroxide in second ionogen, and forms hydrochloric acid in first ionogen.
54. the method for claim 41 wherein applies 0.1V or lower voltage between anode and negative electrode.
55. the method for claim 41 wherein applies the voltage of 0.1～0.4V between anode and negative electrode.
56. the method for claim 41 wherein applies 0.1～0.6V or lower voltage between anode and negative electrode.
57. the method for claim 41 does not wherein form oxygen at the anode place.
58. the method for claim 41 does not wherein form chlorine at the negative electrode place.
59. the method for claim 41, it further comprises carbonic acid gas is dissolved in second ionogen.
60. the method for claim 59, it further comprises makes second ionogen contact with the solution that comprises alkaline-earth metal ions.
61. the method for claim 60, wherein this second ionogen comprises carbonate ion.
62. the method for claim 61, it further is included in second ionogen and precipitates alkaline carbonate.
63. an electrochemical method, it comprises:
Between anode and negative electrode, apply voltage, wherein
(i) this anode contacts with first ionogen, and this first ionogen contacts with anion-exchange membrane again;
(ii) this negative electrode contacts with second ionogen, and this second ionogen contacts with cationic exchange membrane again;
(iii) the 3rd ionogen is between anion-exchange membrane and cationic exchange membrane,
Form hydroxide ion thus at the negative electrode place, do not form gas at the anode place simultaneously.
64. the method for claim 63, wherein the 3rd ionogen comprises sodium-chlor, and first and second ionogen comprise salt solution, and it comprises seawater, fresh water, brackish water or slightly salty.
65. the method for claim 63, wherein chlorion from the 3rd electrolyte to first ionogen; Sodium ion is moved to second ionogen; Form hydrogen at the negative electrode place; And form proton at the anode place.
66. the method for claim 63, anode wherein leads hydrogen.
67. the method for claim 65 wherein forms sodium hydroxide in second ionogen, and forms hydrochloric acid in first ionogen.
68. the method for claim 63 wherein applies the voltage of 0.1～0.4V between anode and negative electrode.
69. the method for claim 63 wherein applies 0.1～0.6V or lower voltage between anode and negative electrode.
70. the method for claim 63 does not wherein form oxygen at the anode place.
71. the method for claim 63 does not wherein form chlorine at the negative electrode place.
72. the method for claim 63, it further comprises carbonic acid gas is dissolved in second ionogen.
73. the method for claim 72, it further comprises makes second ionogen contact with the solution that comprises alkaline-earth metal ions.
74. the method for claim 73, wherein this second ionogen comprises carbonate ion.
75. the method for claim 74, it further is included in second ionogen and precipitates alkaline earth metal carbonate.
76. the method for claim 73 wherein applies the voltage of 0.1～1.0V between anode and negative electrode.
77. the method for claim 41 wherein applies the voltage of 0.1～1.0V between anode and negative electrode.
78. the method for claim 25 wherein applies the voltage of 0.1～1.0V between anode and negative electrode.
79. the method for claim 41 wherein applies 0.1V or lower voltage between anode and negative electrode.
80. the method for claim 63 wherein applies 0.1V or lower voltage between anode and negative electrode.
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